Multiple Effects Tailoring the Self-organization Behaviors of Triphenylene Side-chain Liquid Crystalline Polymers via Changing the Spacer Length

Long-alkyl tail triphenylene (TP) side-chain liquid crystalline polymers (SCLCPs) with different spacer length (P- m -TP, m = 2, 3, 4, 6, 8, which is the number of carbon atom in the flexible alkyl spacers) have been successfully synthesized via free radical polymerization. The differential scanning calorimetry (DSC), polarized light microscopy (POM), ultraviolet-visible spectroscopy (UV-Vis), wide-angle X-ray diffraction (WAXD) and small-angle X-ray scattering (SAXS) measurements were performed to investigate the influence of multiple effects on the self-organization behaviors of P- m -TP, including steric effect, decoupling effect and π - π stacking effect. The experimental results revealed that P- m -TP ( m = 2, 3, 4) formed the columnar phase which was developed by the TP moieties and the main chain as a whole, suggesting that the side-chains had strong steric effect even though the number of spacer length ( m ) exceeded 4. In addition, the clearing points ( T i s) of the polymers were above 300 °C. When m = 6 and 8, the polymers displayed hexagonal columnar phase and exhibited the low T i s (91 and 80 °C respectively), originating from the self-assembly of triphenylene due to the decoupling effect and π - π stacking effect. This work offers a viable and inspiring pathway to control the phase transition temperature and phase structure of TP SCLCPs via simply tailoring the spacer length and increasing the alkyl tail length of TP.